CN106268852A - A kind of catalyst for one-step method from syngas coproduction mixed alcohol and alhpa olefin and preparation method and application - Google Patents

A kind of catalyst for one-step method from syngas coproduction mixed alcohol and alhpa olefin and preparation method and application Download PDF

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CN106268852A
CN106268852A CN201610554223.1A CN201610554223A CN106268852A CN 106268852 A CN106268852 A CN 106268852A CN 201610554223 A CN201610554223 A CN 201610554223A CN 106268852 A CN106268852 A CN 106268852A
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temperature
carbonization
reduction
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CN106268852B (en
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孙予罕
林铁军
钟良枢
于飞
齐行振
卢卫民
李克健
李晋平
肖亚宁
刘斌
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China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Advanced Research Institute of CAS
Shanxi Luan Environmental Energy Development Co Ltd
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China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Advanced Research Institute of CAS
Shanxi Luan Environmental Energy Development Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/22—Carbides

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Abstract

The present invention provides a kind of catalyst for one-step method from syngas coproduction mixed alcohol and alhpa olefin and preparation method and application.This catalyst includes following components: Co3O4, Co accounts for the 10 ~ 60% of catalyst gross mass；The steady oxide of M1, M1 accounts for the 0 ~ 5% of catalyst gross mass；The steady oxide of M2, M2 accounts for the 10 ~ 60% of catalyst gross mass；One or more in Li, Na, K, Rb and Cs of M1, one or more in Mg, Ca, Zn, Al, Zr, Mn, La and Ce of M2.This catalyst obtains the catalyst activity component for one-step method from syngas coproduction mixed alcohol and alhpa olefin through reduction activation and carbonization, and this active component is Co2C nano particle.This preparation method is simple, and the catalyst stability obtained is good, and in one-step method from syngas coproduction mixed alcohol and alhpa olefin, the carbon number selectivity of mixed alcohol and alhpa olefin is high, and methane selectively is low.

Description

A kind of for one-step method from syngas coproduction mixed alcohol and the catalyst of alpha-olefin and system Preparation Method and application
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of for one-step method from syngas coproduction mixed alcohol and α- Catalyst of alkene and preparation method and application.
Background technology
In recent years, along with the scarcity day by day of Global Oil resource, coal and natural gas will gradually replace oil becomes following energy The main supply form in source.China is the developing country of the few oily many gas of a rich coal, improves colliery and natural gas at China's energy Proportion in source structure is beneficial to the healthy and sustainable development of Chinese national economy, and is to ensure that the important of Chinese energy safety Strategic measure.Instantly China's energy environment issues highlights, and energy utilization rate is low, and the clean and effective improving coal utilizes and natural gas High value added product be an important path of China's energy development from now on.
C1 chemical industry based on syngas catalytic conversion is to realize coal and the important channel of natural gas clean and effective conversion. Instantly, based on syngas catalytic conversion, the industrialization having been carried out reaction includes F-T synthesis, methanol-fueled CLC, methanol-to-olefins Deng.With synthesis gas as unstripped gas, catalyzed conversion prepares long-chain olefin and mixed alcohol is realize synthesis gas high added value important Path, is also the next one of the syngas catalytic conversion technology path with potential prospects for commercial application.So-called long-chain olefin Referring to that molecule contains more than 5 carbon atoms and the aliphatic hydrocarbon of a carbon-to-carbon double bond, its formula is CnH2n.According to position of double bond Difference is divided into end alkene (alpha-olefin) and internal olefin.It is contour additional that long-chain olefin can be used for synthesizing bigh carbon alcohol, long chain mercaptans, lubricating oil Value chemicals, is widely used in petrochemical industry, light industry, weaving, metallurgy and the aspect such as medicine, pesticide.Traditional petroleum path method It is difficult to obtain long-chain alpha-olefin, the long-chain olefin of especially single carbon number, and syngas catalytic conversion path can obtain with one-step method The long-chain alpha-olefin of different carbon number distribution, has that flow process is short, that energy consumption is low is specific.So-called mixed alcohol refers to comprise not in product Monohydric alcohol with carbon number.Mixed alcohol, especially higher alcohols have wide economic worth and application prospect, both can be direct Fuel as the modern means of communication, it is also possible to add extremely as fuel, especially as the intermediate product of fine chemical product, extensively General it is applied to the fields such as surfactant, plasticizer, detergent and cosmetics.Traditional mixed alcohol production method mainly has chemistry Synthesis or oil hydrogenation method.The former transition depends on petroleum resources, and it is high and secondary to there is reaction process length, technical sophistication, cost The shortcomings such as reaction is many；The latter is limited to raw material supply and is difficult to large-scale industrial production.Visible, development may replace traditional preparation methods Synthetic route most important.
Using synthesis gas method a step can obtain mixed alcohol and alpha-olefin, this path has extremely important economic worth. Prepare the conventional catalyst system of mixed alcohol currently, with respect to synthesis gas and mainly have modified methanol catalyst, modified FT catalyst, molybdenum Base catalyst and Rh base catalyst；The catalyst system and catalyzing conventional about alkene synthesis is mainly Fe base and Co base.But, traditional this A little catalyst system and catalyzings are unsatisfactory at aspects such as activity, selectivity, stability and economy, to such an extent as to this route fails to realize industry Change.Research and development high activity, high selectivity, the new catalyst simultaneously having excellent Repeatability and stability concurrently is most important. In the present invention, we report a kind of cobalt-base catalyst, can obtain stable cobalt carbide activity by reduction and carbonization treatment Species, under the reaction condition optimized, can convert coproduction mixed alcohol and alkene by efficient catalytic.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide and mix for one-step method from syngas coproduction Close catalyst of alcohol and alpha-olefin and preparation method and application.The catalyst of the present invention is at synthesis gas coproduction mixed alcohol and α-alkene The course of reaction of hydrocarbon has the advantages such as high activity, high carbon number selectivity and catalyst life length.Due to method for preparing catalyst letter Single, be prone to repeat, be conducive to industry to amplify.
For achieving the above object and other relevant purposes, first aspect present invention provides one to join for one-step method from syngas Producing mixed alcohol and the catalyst of alpha-olefin, described catalyst includes following components:
Co3O4, Co accounts for the 10～60% of catalyst gross mass；Preferably, 20～50%；
The steady oxide of M1, M1 accounts for the 0～5% of catalyst gross mass；Preferably, 0～1.5%；
The steady oxide of M2, M2 accounts for the 10～60% of catalyst gross mass；Preferably, 20～50%；
One or more in Li, Na, K, Rb and Cs of M1, M2 is in Mg, Ca, Zn, Al, Zr, Mn, La and Ce One or more.
The steady oxide of Li is Li2O；The steady oxide of Na is Na2O；The steady oxide of K is K2O；Rb stablizes Oxide is Rb2O；The steady oxide of Cs is Cs2O；The steady oxide of Mg is MgO；The steady oxide of Ca is CaO；Zn's Steady oxide is ZnO；The steady oxide of Al is Al2O3；The steady oxide of Zr is ZrO2；The steady oxide of Mn is MnO2；The steady oxide of La is La2O3；The steady oxide of Ce is CeO2。
Second aspect present invention provides the preparation method of above-mentioned catalyst, comprises the steps:
(1) according to catalyst composition and ratio, the slaine of cobalt salt Yu M2 is mixed to get mixing salt solution；
(2) according to catalyst composition and ratio, precipitant and water are mixed to get precipitant aqueous solution；
(3) precipitant aqueous solution stream that mixing salt solution step (1) obtained and step (2) obtain carry out coprecipitated Form sediment；
(4) mixture that step (3) obtains is carried out aging；
(5) mixture (5A) as steps described below step (4) obtained or (5B) are carried out, and i.e. obtain described catalyst:
(5A): separate, wash, be dried and roasting；
(5B): separating, wash, obtain catalyst precursor after drying, the slaine that catalyst precursor impregnates M1 is molten Liquid, drying, roasting, obtain catalyst.
It is highly preferred that in step (3), the precipitant that mixing salt solution step (1) obtained and step (2) obtain is water-soluble Liquid uses and the mode that flows instills in water.
Preferably, also include any one of following characteristics or multinomial:
(1), in step (1), the concentration of total slaine of described mixing salt solution is 0.1～5mol/L；
(2) in step (1), slaine one in chlorate, nitrate, sulfate, carbonate and acetate or Multiple；
(3), in step (2), the concentration of precipitant aqueous solution is 0.1～5mol/L；
(4), in step (2), described precipitant is selected from Na2CO3、K2CO3、(NH4)2CO3, NaOH, KOH and NH3·H2In O One or more；
(5) in step (3), the condition of co-precipitation is: pH is 6～10, and temperature is 0～80 DEG C；
(6) in step (4), aging condition is: aging temperature is 0～80 DEG C, and ageing time is 0.5～24h.
(7) in step (5A), baking temperature is 80～120 DEG C, and sintering temperature is 250～600 DEG C, roasting time be 2～ 10h；
(8) in step (5B), baking temperature is 80～120 DEG C, and sintering temperature is 250～600 DEG C, roasting time be 2～ 10h。
Third aspect present invention provides the purposes of above-mentioned catalyst, for one-step method from syngas coproduction mixed alcohol and α-alkene Hydrocarbon.
Preferably, before one-step method from syngas coproduction mixed alcohol and alpha-olefin, following steps are first being carried out: right wanted Ask the reduction activation in reducing atmosphere of the catalyst described in 1, then carbonization in carburizing atmosphere.
Preferably, also include any one of following characteristics or multinomial:
(1) one or more in hydrogen, CO, dilution hydrogen, dilution CO and dilution synthesis gas of reducing atmosphere, dilution Gas is noble gas, and diluent gas volume content is less than 90%；
It is highly preferred that synthesis gas is made up of CO and hydrogen, H2It is 0.5～5 with the mol ratio of CO, preferably 0.5～2；
It is highly preferred that described noble gas is nitrogen, argon or helium；
(2) condition of reduction activation is: reduction temperature is 200～500 DEG C, and the recovery time is 2～10h, and reduction air speed is 1000～20000ml g-1·h-1, reduction pressure is normal pressure；
(3) one or more in CO, synthesis gas, dilution CO and dilution synthesis gas of carburizing atmosphere, diluent gas is Noble gas, diluent gas volume content is less than 90%；
It is highly preferred that synthesis gas is made up of CO and hydrogen, H2It is 0.5～5 with the mol ratio of CO, preferably 0.5～2；
It is highly preferred that described noble gas is nitrogen, argon or helium；
(4) carburizing temperature is 200～400 DEG C, preferably 200～300 DEG C, and carbonization time is 24～240h, preferably 36 ～120h, carbonization gas air speed is 1000～20000ml g-1·h-1, carbonization pressure is normal pressure～6MPa, preferably 0.1～ 2MPa。
Preferably, for one-step method from syngas coproduction mixed alcohol and alpha-olefin, reaction condition is: the unstripped gas that reaction uses H2/ CO mol ratio is 0.5～5, preferably 0.5～2, and reaction temperature is 200 DEG C～300 DEG C, and reaction pressure is normal pressure～6MPa, Reaction velocity is 500～10000ml g-1·h-1。
It is highly preferred that described reaction is carried out in fixed bed or slurry bed system.
Fourth aspect present invention provides a kind of for one-step method from syngas coproduction mixed alcohol and the catalyst activity of alpha-olefin Component, described active component is Co2C nano particle, described Co2The above-mentioned catalyst reduction activation in reducing atmosphere of C nano particle Obtain with in carbonization in carburizing atmosphere.M1 and M2 contributes to the formation of cobalt carbide and stablizes, M1 and M2 is with oxide or compound Oxide form is present in Co2In C nano particle.
Fifth aspect present invention provides the preparation method of above-mentioned catalyst activity component, comprises the steps: to urge above-mentioned Agent is reduction activation in reducing atmosphere, then carbonization in carburizing atmosphere.
Preferably, also include any one of following characteristics or multinomial:
(1) one or more in hydrogen, CO, dilution hydrogen, dilution CO and dilution synthesis gas of reducing atmosphere, dilution Gas is noble gas, and diluent gas volume content is less than 90%；
It is highly preferred that synthesis gas is made up of CO and hydrogen, H2It is 0.5～5 with the mol ratio of CO, preferably 0.5～2；
It is highly preferred that described noble gas is nitrogen, argon or helium；
(2) condition of reduction activation is: reduction temperature is 200～500 DEG C, and the recovery time is 2～10h, and reduction air speed is 1000～20000ml mg-1·h-1, reduction pressure is normal pressure；
(3) one or more in CO, synthesis gas, dilution CO and dilution synthesis gas of carburizing atmosphere, diluent gas is Noble gas, diluent gas volume content is less than 90%；
It is highly preferred that synthesis gas is made up of CO and hydrogen, H2It is 0.5～5 with the mol ratio of CO, preferably 0.5～2；
It is highly preferred that described noble gas is nitrogen, argon or helium；
(4) carburizing temperature is 200～400 DEG C, preferably 200～300 DEG C, and carbonization time is 24～240h, preferably 36 ～120h, carbonization gas air speed is 1000～20000ml g-1·h-1, carbonization pressure is normal pressure～6MPa, preferably 0.1～ 2MPa。
Fifth aspect present invention provides the purposes of above-mentioned catalyst activity component, for one-step method from syngas coproduction mixed alcohol And alpha-olefin, reaction condition is: the unstripped gas H that reaction uses2/ CO mol ratio is 0.5～5, preferably 0.5～2, reaction temperature Being 200 DEG C～300 DEG C, reaction pressure is normal pressure～6MPa, and reaction velocity is 500～10000ml g-1·h-1。
It is highly preferred that described reaction is carried out in fixed bed or slurry bed system.
Synthesis gas coproduction mixed alcohol that the present invention provides and the method for preparing catalyst of alkene, have reaction process simple, The advantages such as the stability of catalyst is good, in product, alfin total carbon number selectivity is higher than 90%, wherein, C in alcohol product2 +OH mass Percentage composition reaches more than 90%, simultaneously alkene/alkane ratio up to more than 10, has higher economic benefit and extremely strong commercial Application Prospect.
The present invention provides a kind of catalyst for one-step method from syngas coproduction mixed alcohol and alpha-olefin and preparation method thereof With application.Described catalyst includes following components: CoO, Co account for the 10～60% of catalyst gross mass；The steady oxide of M1, M1 accounts for the 0～5% of catalyst gross mass；The steady oxide of M2, M2 accounts for the 10～60% of catalyst gross mass；M1 selected from Li, One or more in Na, K, Rb and Cs, one or more in Mg, Ca, Zn, Al, Zr, Mn, La and Ce of M2.Described urge Agent in reducing atmosphere reduction activation and in carburizing atmosphere carbonization obtain for one-step method from syngas coproduction mixed alcohol and α- The catalyst activity component of alkene, described active component is Co2C nano particle.The synthesis gas coproduction mixed alcohol that the present invention provides Simple with the method for preparing catalyst of alpha-olefin and reaction process, the carbon number selectivity of this catalyst mixed alcohol and alpha-olefin is high, Methane selectively is low, and reaction condition is gentle, and catalyst stabilization performance is good, the inclined long-chain of product, main in this catalyst liquid product For alcohol and the alkene of high carbon number, product added value is high, and in product, alfin carbon selectivity is higher than 90%, wherein, C in alcohol product2 + OH weight/mass percentage composition reaches more than 90%, simultaneously C12 +Alkene/alkane ratio up to more than 10, has higher economic worth and potential Prospects for commercial application.
Accompanying drawing explanation
The XRD figure of Fig. 1 cobalt carbide catalyst.
The 1000h study on the stability result of Fig. 2 cobalt carbide catalyst.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by this specification Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by the most different concrete realities The mode of executing is carried out or applies, the every details in this specification can also based on different viewpoints and application, without departing from Various modification or change is carried out under the spirit of the present invention.
[embodiment 1]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 2mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 2mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt% (to refer to that M1 accounts for catalyst The percentage ratio of gross mass, following example are identical, i.e. M1 is sodium, account for the 1wt% of catalyst gross mass), it is placed in again after air-drying 120 DEG C of baking ovens are dried, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization Air speed 10000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% conjunction Become gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity is 2000ml g-1·h-1, instead Answering pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 2]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 2mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 2mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with potassium carbonate for impregnation liquid slaine presoma, uses the potassium of incipient impregnation 1wt%, is placed in after air-drying again 120 DEG C of baking ovens are dried, is finally transferred to Muffle furnace Program and is warming up to 400 DEG C of roasting 5h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization Air speed 10000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% conjunction Become gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 260 DEG C, reaction velocity is 2000ml g-1·h-1, instead Answering pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 3]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 0.5mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, shape Becoming concentration is 0.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=8, by above two solution by and flow Mode is co-precipitated.Titration terminate after at 65 DEG C aging 6h, by centrifugation, washing be that neutrality is placed on 100 DEG C of baking ovens to pH Middle drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt%, after air-drying again It is placed in 120 DEG C of baking ovens drying, is finally transferred to Muffle furnace Program and is warming up to 400 DEG C of roasting 5h.I.e. urged after roasting is complete Agent.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization Air speed 10000ml g-1·h-1, carbonization pressure 0.1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% Synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 270 DEG C, reaction velocity is 2000ml g-1·h-1, Reaction pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 4]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=0.5/1 in molar ratio is dissolved in a certain amount of going In ionized water, form the mixed solution that total metal concentration is 1mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, shape Becoming concentration is 1mol/L alkali liquor.Regulation titration temperature is 60 DEG C, controls titration pH=8, by above two solution by and the side flowed Formula is co-precipitated.Titration terminate after at 60 DEG C aging 6h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens to pH Dry 12h, be finally transferred to Muffle furnace Program and be warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 6h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=2) carbonization, carburizing temperature 300 DEG C, carbonization time 72h, carbonization is empty Speed 20000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis Gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity is 2000ml g-1·h-1, reaction Pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 5]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 3mol/L, then potassium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 3mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with potassium carbonate for impregnation liquid slaine presoma, uses the potassium of incipient impregnation 1wt%, is placed in after air-drying again 120 DEG C of baking ovens are dried, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization Air speed 10000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% conjunction Become gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity is 2000ml g-1·h-1, instead Answering pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 6]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 2mol/L, then ammonium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 2mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt%, is placed in after air-drying again 120 DEG C of baking ovens are dried, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization Air speed 10000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% conjunction Become gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity is 2000ml g-1·h-1, instead Answering pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 7]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Al (NO3)2·6H2O Co/Mn/Al=2/ in molar ratio 1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then is dissolved in by sodium carbonate In a certain amount of deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=9, will Above two solution by and the mode that flows be co-precipitated.Titration terminate after at 65 DEG C aging 3h, by centrifugation, washing to pH be Neutrality is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses incipient impregnation The sodium of 0.8wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 250 DEG C, carbonization time 96h, carbonization air speed 5000ml·g-1·h-1, carbonization pressure 1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 265 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure Power is 1MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 8]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Zr (NO3)4·5H2O Co/Mn/Al=2/ in molar ratio 1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then is dissolved in by sodium carbonate In a certain amount of deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=9, will Above two solution by and the mode that flows be co-precipitated.Titration terminate after at 65 DEG C aging 3h, by centrifugation, washing to pH be Neutrality is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses incipient impregnation The sodium of 0.8wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 250 DEG C, carbonization time 96h, carbonization air speed 5000ml·g-1·h-1, carbonization pressure 1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 255 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure Power is 1MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 9]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Al (NO3)2·6H2O Co/Mn/Al=2/ in molar ratio 1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then is dissolved in by sodium carbonate In a certain amount of deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 30 DEG C, controls titration pH=9, will Above two solution by and the mode that flows be co-precipitated.Titration terminate after at 30 DEG C aging 2h, by centrifugation, washing to pH be Neutrality is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses incipient impregnation The sodium of 0.8wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% synthesis gas (H2/ CO=0.2), reduction air speed is 20000ml g-1·h-1, reduction temperature is 300 DEG C, and the recovery time is 5h.After reduction process terminates and temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 200 DEG C, during carbonization Between 120h, carbonization air speed 2000ml g-1·h-1, carbonization pressure 2MPa.After carbonization terminates and after temperature is down to room temperature, switching Become 100% synthesis gas (H2/ CO=2), it is as follows that reaction condition is set: reaction temperature is 230 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure is 2MPa, H2Mol ratio=2 of/CO, reaction result is as shown in table 1.
[embodiment 10]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Al (NO3)2·6H2O Co/Mn/Al=2/ in molar ratio 1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then is dissolved in by sodium carbonate In a certain amount of deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 30 DEG C, controls titration pH=9, will Above two solution by and the mode that flows be co-precipitated.Titration terminate after at 30 DEG C aging 2h, by centrifugation, washing to pH be Neutrality is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses incipient impregnation The sodium of 0.8wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% synthesis gas (H2/ CO=0.2), reduction air speed is 20000ml g-1·h-1, reduction temperature is 300 DEG C, and the recovery time is 5h.After reduction process terminates and temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 200 DEG C, during carbonization Between 120h, carbonization air speed 2000ml g-1·h-1, carbonization pressure 2MPa.After carbonization terminates and after temperature is down to room temperature, switching Become 100% synthesis gas (H2/ CO=2), it is as follows that reaction condition is set: reaction temperature is 230 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure is 4MPa, H2Mol ratio=2 of/CO, reaction result is as shown in table 1.
[embodiment 11]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O、Zn(NO3)2·9H2O and Zr (NO3)4·5H2O by mole It is dissolved in a certain amount of deionized water than Co/Mn/Zn/Zr=2/1/1/0.2, forms the mixing that total metal concentration is 1.5mol/L Solution, then sodium carbonate is dissolved in a certain amount of deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, control titration pH=7, by above two solution by and the mode that flows be co-precipitated.Titration is aging at 65 DEG C after terminating 3h, by centrifugation, washing to pH be neutrality be placed in 100 DEG C of baking ovens drying 12h, be finally transferred to Muffle furnace Program and be warming up to 350 DEG C of roasting 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% synthesis gas (H2/ CO=2), reduction air speed is 20000ml g-1·h-1, reduction temperature is 300 DEG C, and the recovery time is 5h. After reduction process terminates and temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 200 DEG C, carbonization time 120h, carbonization air speed 2000ml g-1·h-1, carbonization pressure 2MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=2), it is as follows that reaction condition is set: reaction temperature is 240 DEG C, reaction velocity is 3000ml g-1· h-1, reaction pressure is 6MPa, H2Mol ratio=2 of/CO, reaction result is as shown in table 1.
[embodiment 12]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Mg (NO3)2·6H2O Co/Mn/Mg=2/ in molar ratio 1/1 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then ammonium carbonate is dissolved in one In quantitative deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=8, by upper State two kinds of solution by and the mode that flows be co-precipitated.Titration terminate after at 65 DEG C aging 4h, by centrifugation, washing to pH be Property be placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, use incipient impregnation The sodium of 0.6wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10%H2, reduction air speed is 5000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminates and temperature After degree is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 250 DEG C, carbonization time 96h, carbonization air speed 8000ml·g-1·h-1, carbonization pressure 1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 260 DEG C, reaction velocity is 4000ml g-1·h-1, reaction pressure Power is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 13]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and La (NO3)3·6H2O Co/Mn/La=2/ in molar ratio 1/1 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 1.5mol/L, then ammonium carbonate is dissolved in one In quantitative deionized water, forming concentration is 1.5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=8, by upper State two kinds of solution by and the mode that flows be co-precipitated.Titration terminate after at 65 DEG C aging 4h, by centrifugation, washing to pH be Property be placed in 100 DEG C of baking ovens drying 12h, then with cesium carbonate for impregnation liquid slaine presoma, use incipient impregnation The caesium of 0.6wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10%CO, reduction air speed is 5000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminate and After temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 250 DEG C, carbonization time 96h, carbonization air speed 8000ml·g-1·h-1, carbonization pressure 1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 260 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure Power is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 14]
By Co (NO3)2·6H2O、Al(NO3)2·6H2O、Zn(NO3)2·9H2O and Zr (NO3)4·5H2O Co/ in molar ratio Al/Zn/Zr=3/1/1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 2mol/L, then Being dissolved in a certain amount of deionized water by ammonium carbonate, forming concentration is 2mol/L alkali liquor.Regulation titration temperature is 70 DEG C, controls to drip Determine pH=8, by above two solution by and the mode that flows be co-precipitated.Titration terminate after at 70 DEG C aging 2h, by centrifugation, Washing to pH is that neutrality is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses The sodium of incipient impregnation 1.2wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program liter Warm to 350 DEG C of roasting 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take the thin SiC of 1.5g with 3.0g and mix.This catalysis Agent is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases 10%H2, Reduction air speed is 8000ml g-1·h-1, reduction temperature is 300 DEG C, and the recovery time is 5h.Reduction process terminates and temperature is down to After room temperature, use CO carbonization, carburizing temperature 200 DEG C, carbonization time 120h, carbonization air speed 8000ml g-1·h-1, carbonization pressure 0.5MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=1), reaction condition is set As follows: reaction temperature is 270 DEG C, reaction velocity is 4000ml g-1·h-1, reaction pressure is 0.5MPa, H2The mol ratio of/CO =1, reaction result is as shown in table 1.
[embodiment 15]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=2/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 2mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 2mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with rubidium carbonate for impregnation liquid slaine presoma, uses the rubidium of incipient impregnation 0.6wt%, puts after air-drying again Dry in 120 DEG C of baking ovens, be finally transferred to Muffle furnace Program and be warming up to 300 DEG C of roasting 3h.I.e. it is catalyzed after roasting is complete Agent.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take the thin SiC of 1.5g with 3.0g and mix.This catalysis Agent is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases 10% hydrogen Gas, reduction air speed is 2000ml g-1·h-1, reduction temperature is 250 DEG C, and the recovery time is 10h.Reduction process terminates and temperature After being down to room temperature, use 50%CO carbonization, carburizing temperature 250 DEG C, carbonization time 72h, carbonization air speed 8000ml g-1·h-1, carbon Change pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), arrange anti- Answering condition as follows: reaction temperature is 260 DEG C, reaction velocity is 6000ml g-1·h-1, reaction pressure is 0.5MPa, H2/ CO's Mol ratio=0.5, reaction result is as shown in table 1.
[embodiment 16]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O、Ca(NO3)2·4H2O、Ce(NO3)3·6H2O is in molar ratio Co/Mn/Ca/Ce=4/1/1/0.5 is dissolved in a certain amount of deionized water, forms the mixing that total metal concentration is 0.1mol/L molten Liquid, then ammonium carbonate is dissolved in a certain amount of deionized water, forming concentration is 0.1mol/L alkali liquor.Regulation titration temperature is 80 DEG C, control titration pH=10, by above two solution by and the mode that flows be co-precipitated.Titration is aging at 80 DEG C after terminating 0.5h, by centrifugation, washing to pH be neutrality be placed in 80 DEG C of baking ovens drying 24h, then with lithium nitrate for impregnation liquid slaine Presoma, uses the Li of incipient impregnation 0.01wt%, is placed in 120 DEG C of baking ovens drying again, is finally transferred to horse after air-drying Not stove Program is warming up to 500 DEG C of roasting 2h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take the thin SiC of 1.5g with 3.0g and mix.This catalysis Agent is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is closed with 10% Become gas (H2/ CO=2), reduction air speed is 1000ml g-1·h-1, reduction temperature is 500 DEG C, and the recovery time is 4h.Reduction process After end and temperature are down to 400 DEG C, with pure CO carbonization, carburizing temperature 400 DEG C, carbonization time 24h, carbonization pressure 6MPa, carbonization Air speed 1000ml g-1·h-1.After carbonization terminates and after temperature is down to 210 DEG C, it is depressurized to 1.5MPa, switches to 100% conjunction Become gas (H2/ CO=2), it is as follows that reaction condition is set: reaction temperature is 210 DEG C, reaction velocity is 500ml g-1·h-1, reaction Pressure is 1.5MPa, H2Mol ratio=2 of/CO, reaction result is as shown in table 1.
[embodiment 17]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Al (NO3)2·6H2O Co/Mn/Al=3/ in molar ratio 1/1 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 0.2mol/L, then ammonium carbonate is dissolved in one In quantitative deionized water, forming concentration is 0.2mol/L alkali liquor.Under ice bath, titrate (titration temperature is 2 DEG C), control titration PH=7, by above two solution by and the mode that flows be co-precipitated.Titration terminate after under ice bath aging 10h, by centrifugation, Washing to pH is that neutrality is placed in 120 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses The sodium of incipient impregnation 2wt%, is placed in 120 DEG C of baking ovens drying after air-drying again, is finally transferred to Muffle furnace Program and heats up To 600 DEG C of roasting 3h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 1000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminates Rear cutout uses synthesis gas (H instead2/ CO=0.2) carbonization, carburizing temperature 350 DEG C, carbonization time 100h, carbonization air speed 1000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO= 0.5), arranging reaction condition as follows: reaction temperature is 265 DEG C, reaction velocity is 10000ml g-1·h-1, reaction pressure is normal Pressure, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 18]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 0.5mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, shape Becoming concentration is 0.5mol/L alkali liquor.Regulation titration temperature is 2 DEG C (ice baths), controls titration pH=8, by above two solution by also The mode of stream is co-precipitated.Titration terminate after under ice bath aging 24h, by centrifugation, washing be that neutrality is placed on 100 DEG C to pH Baking oven is dried 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt%, wait to air-dry After be placed in 120 DEG C of baking ovens drying again, be finally transferred to Muffle furnace Program and be warming up to 250 DEG C of roasting 10h.After roasting is complete and get final product To catalyst.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10%CO, reduction air speed is 8000ml g-1·h-1, reduction temperature is 200 DEG C, and the recovery time is 10h.Reduction process terminate and After temperature is down to room temperature, use CO carbonization, carburizing temperature 300 DEG C, carbonization time 240h, carbonization air speed 8000ml g-1·h-1, carbon Change pressure 0.2MPa.100% synthesis gas (H is switched to after carbonization terminates2/ CO=2), it is as follows that reaction condition is set: reaction temperature Degree is 200 DEG C, and reaction velocity is 500ml g-1·h-1, reaction pressure is 0.2MPa, H2Mol ratio=2 of/CO, reaction result As shown in table 1.
[embodiment 19]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O and Zr (NO3)4·5H2O Co/Mn/Zr=2/ in molar ratio 1/0.5 is dissolved in a certain amount of deionized water, forms the mixed solution that total metal concentration is 5mol/L, then sodium carbonate is dissolved in one In quantitative deionized water, forming concentration is 5mol/L alkali liquor.Regulation titration temperature is 65 DEG C, controls titration pH=9, by above-mentioned Two kinds of solution by and the mode that flows be co-precipitated.Titration terminate after at 65 DEG C aging 3h, by centrifugation, washing to pH be neutrality It is placed in 100 DEG C of baking ovens drying 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses incipient impregnation The sodium of 0.8wt%, is placed in 120 DEG C of baking ovens drying again after air-drying, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roastings Burn 6h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 350 DEG C, and the recovery time is 5h.Reduction process terminates And after temperature is down to room temperature, with synthesis gas (H2/ CO=0.2) carbonization, carburizing temperature 250 DEG C, carbonization time 96h, carbonization air speed 5000ml·g-1·h-1, carbonization pressure 1MPa.After carbonization terminates and after temperature is down to room temperature, switch to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 255 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure Power is 1MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 20]
By 50%Mn (NO3)2Aqueous solution and Co (NO3)2·6H2O Co/Mn=3/1 in molar ratio be dissolved in a certain amount of go from In sub-water, form the mixed solution that total metal concentration is 2mol/L, then sodium carbonate is dissolved in a certain amount of deionized water, formed Concentration is 2mol/L alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows It is co-precipitated.Titration terminate after at 40 DEG C aging 4h, by centrifugation, washing be that neutrality is placed in 100 DEG C of baking ovens baking to pH Dry 12h, then with sodium carbonate for impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt%, is placed in after air-drying again 120 DEG C of baking ovens are dried, is finally transferred to Muffle furnace Program and is warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
By the catalyst fines tabletting after roasting and be crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand and mix.Should Catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixed bed reactors.Reducing gases is used 10% hydrogen (He gas is as diluent gas), reduction air speed is 10000ml g-1·h-1, reduction temperature is 400 DEG C, during reduction Between be 5h.After reduction process terminates and temperature is down to room temperature, with 50% synthesis gas (H2/ CO=0.5) carbonization, carburizing temperature 300 DEG C, carbonization time 48h, carbonization air speed 10000ml g-1·h-1, carbonization pressure normal pressure.After carbonization terminates and temperature is down to room Wen Hou, switches to 100% synthesis gas (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity For 2000ml g-1·h-1, reaction pressure is 0.5MPa, H2Mol ratio=0.5 of/CO, reaction result is as shown in table 1.
[embodiment 21]
By 50%Mn (NO3)2Aqueous solution, Co (NO3)2·6H2O、Al(NO3)2·6H2O、Mg(NO3)2·6H2O and Zn (NO3)2·9H2O Co/Mn/Al/Mg/Zn=3/1/1/0.5/0.1 in molar ratio is dissolved in a certain amount of deionized water, is formed total Metal concentration is the mixed solution of 2mol/L, then is dissolved in a certain amount of deionized water by sodium carbonate, and forming concentration is 2mol/L Alkali liquor.Regulation titration temperature is 40 DEG C, controls titration pH=8, by above two solution by and the mode that flows be co-precipitated.Drip Fixed terminate after at 40 DEG C aging 4h, by centrifugation, washing to pH be that neutrality is placed in 100 DEG C of baking ovens drying 12h, then with carbon Acid sodium is impregnation liquid slaine presoma, uses the sodium of incipient impregnation 1wt%, is placed in 120 DEG C of baking ovens baking again after air-drying Dry, finally it is transferred to Muffle furnace Program and is warming up to 350 DEG C of roasting 4h.Catalyst is i.e. obtained after roasting is complete.
Catalyst fines after roasting is mixed with silicon carbide powder and tabletting, is crushed to 40～60 mesh, take 1.5g with 3.0g fine quartz sand mixes.This catalyst is in the reaction of synthesis gas coproduction mixed alcohol and alpha-olefin, and reaction unit is fixing Bed reactor.Reducing gases 10% hydrogen, reduction air speed is 10000ml g-1·h-1, reduction temperature is 300 DEG C, the recovery time For 5h.Reduction process terminates and temperature is down to 250 DEG C of switching 50% synthesis gas (H2/ CO=0.5) carry out carbonization, carbonization time 48h, carbonization air speed 10000ml g-1·h-1, carbonization pressure normal pressure.100% synthesis gas is directly switched to after carbonization terminates (H2/ CO=0.5), it is as follows that reaction condition is set: reaction temperature is 250 DEG C, reaction velocity is 2000ml g-1·h-1, reaction pressure Power is 0.1MPa, H2Mol ratio=0.5 of/CO.The XRD spectra of the cobalt carbide catalyst of experiment preparation is as it is shown in figure 1, catalyst 1000h stability test result as shown in Figure 2.
Table 1: embodiment catalyst reaction result
As can be seen from Table 1: use the cobalt carbide catalyst (figure that catalyst described in this patent obtains after reduction and carbonization 1) can the mixed alcohol of coproduction efficiently and alpha-olefin under suitable reaction condition.Specifically: this catalyst (embodiment 7) exists 265 DEG C, 0.5MPa and 2000h-1Under air speed, CO conversion per pass is close to 20%, and corresponding mixed alcohol and the carbon number of alkene select Property is up to 92.3%, and methane is the lowest, and only 3.2%；C2 +Alcohol distribution (C2 +The total carbon number of alcohol accounts for the percentage of oxygenatedchemicals carbon number Number) available 97wt%；And C6 +The percentage composition of alcohol is also up to more than 55%；In alkene/alkane ratio distribution, C3 =/C3Up to 23wt% Above, O/P (C12 +) also it is up to 10.8, illustrate to be partial to long-chain olefin in the distribution of this catalyst product.Cobalt carbide described in this patent Catalyst has mixed alcohol and the alkene coproduction performance of excellence, and its catalytic performance is highly stable, has potential commercial Application Prospect.
The above, only presently preferred embodiments of the present invention, not any formal and substantial to present invention restriction, It should be pointed out that, for those skilled in the art, on the premise of without departing from the inventive method, also can make Some improvement and supplement, these improve and supplement also should be regarded as protection scope of the present invention.All those skilled in the art, Without departing from the spirit and scope of the present invention, make when available disclosed above technology contents a little more The equivalent variations moved, modify and develop, is the Equivalent embodiments of the present invention；Meanwhile, all substantial technological pair according to the present invention The change of any equivalent variations that above-described embodiment is made, modify and develop, all still fall within the scope of technical scheme In.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art All equivalences become are modified or change, and must be contained by the claim of the present invention.

Claims (13)

1. one kind is used for one-step method from syngas coproduction mixed alcohol and the catalyst of alpha-olefin, it is characterised in that described catalyst bag Include following components:
Co3O4, Co accounts for the 10～60% of catalyst gross mass；
The steady oxide of M1, M1 accounts for the 0～5% of catalyst gross mass；
The steady oxide of M2, M2 accounts for the 10～60% of catalyst gross mass；
One or more in Li, Na, K, Rb and Cs of M1, M2 one in Mg, Ca, Zn, Al, Zr, Mn, La and Ce Or it is multiple.
2. the preparation method of catalyst as claimed in claim 1, it is characterised in that comprise the steps:
(1) according to catalyst composition and ratio, the slaine of cobalt salt Yu M2 is mixed to get mixing salt solution；
(2) according to catalyst composition and ratio, precipitant and water are mixed to get precipitant aqueous solution；
(3) the precipitant aqueous solution co-precipitation that mixing salt solution step (1) obtained and step (2) obtain；
(4) mixture that step (3) obtains is carried out aging；
(5) mixture (5A) as steps described below step (4) obtained or (5B) are carried out, and i.e. obtain described catalyst:
(5A): separate, wash, be dried and roasting；
(5B): separate, wash, obtain catalyst precursor after drying, catalyst precursor is impregnated the metal salt solution of M1, warp Dry, roasting, obtains catalyst.
3. preparation method as claimed in claim 2, it is characterised in that also include any one of following characteristics or multinomial:
(1), in step (1), the concentration of total slaine of described mixing salt solution is 0.1～5mol/L；
(2) in step (1), one or more in chlorate, nitrate, sulfate, carbonate and acetate of slaine；
(3), in step (2), the concentration of precipitant aqueous solution is 0.1～5mol/L；
(4), in step (2), described precipitant is selected from Na2CO3、K2CO3、(NH4)2CO3, NaOH, KOH and NH3·H2One in O Or it is multiple；
(5) in step (3), the condition of co-precipitation is: pH is 6～10, and temperature is 0～80 DEG C；
(6) in step (4), aging condition is: aging temperature is 0～80 DEG C, and ageing time is 0.5～24h.
(7) in step (5A), baking temperature is 80～120 DEG C, and sintering temperature is 250～600 DEG C, and roasting time is 2～10h；
(8) in step (5B), baking temperature is 80～120 DEG C, and sintering temperature is 250～600 DEG C, and roasting time is 2～10h.
4. catalyst as claimed in claim 1 is for one-step method from syngas coproduction mixed alcohol and alpha-olefin.
5. purposes as claimed in claim 4, it is characterised in that before one-step method from syngas coproduction mixed alcohol and alpha-olefin First carry out following steps: by the reduction activation in reducing atmosphere of the catalyst described in claim 1, then carbon in carburizing atmosphere Change.
6. purposes as claimed in claim 5, it is characterised in that also include any one of following characteristics or multinomial:
(1) one or more in hydrogen, CO, dilution hydrogen, dilution CO and dilution synthesis gas of reducing atmosphere, diluent gas For noble gas, diluent gas volume content is less than 90%；
(2) condition of reduction activation is: reduction temperature is 200～500 DEG C, and the recovery time is 2～10h, and reduction air speed is 1000 ～20000ml g-1·h-1, reduction pressure is normal pressure；
(3) one or more in CO, synthesis gas, dilution CO and dilution synthesis gas of carburizing atmosphere, diluent gas is inertia Gas, diluent gas volume content is less than 90%；
(4) carburizing temperature is 200～400 DEG C, and carbonization time is 24～240h, and carbonization gas air speed is 1000～20000ml g-1·h-1, carbonization pressure is normal pressure～6MPa.
7. purposes as claimed in claim 5, it is characterised in that for one-step method from syngas coproduction mixed alcohol and alpha-olefin, instead The condition is answered to be: the unstripped gas H that reaction uses2/ CO mol ratio is 0.5～5, and reaction temperature is 200～300 DEG C, and reaction pressure is Normal pressure～6MPa, reaction velocity is 500～10000ml g-1·h-1。
8. purposes as claimed in claim 7, it is characterised in that described reaction is carried out in fixed bed or slurry bed system.
9. one kind is used for one-step method from syngas coproduction mixed alcohol and the catalyst activity component of alpha-olefin, it is characterised in that described Active component is Co2C nano particle, described Co2C nano particle is gone back in reducing atmosphere by the catalyst described in claim 1 Former activation and acquisition in carbonization in carburizing atmosphere.
10. the preparation method of catalyst activity component as claimed in claim 9, it is characterised in that comprise the steps: to weigh Profit requires the reduction activation in reducing atmosphere of the catalyst described in 1, then carbonization in carburizing atmosphere.
11. preparation methoies as claimed in claim 10, it is characterised in that also include any one of following characteristics or multinomial:
(1) one or more in hydrogen, CO, dilution hydrogen, dilution CO and dilution synthesis gas of reducing atmosphere, diluent gas For noble gas, diluent gas volume content is less than 90%；
(2) condition of reduction activation is: reduction temperature is 200～500 DEG C, and the recovery time is 2～10h, and reduction air speed is 1000 ～20000ml g-1·h-1, reduction pressure is normal pressure；
(3) one or more in CO, synthesis gas, dilution CO and dilution synthesis gas of carburizing atmosphere, diluent gas is inertia Gas, diluent gas volume content is less than 90%；
(4) carburizing temperature is 200～400 DEG C, and carbonization time is 24～240h, and carbonization gas air speed is 1000～20000ml g-1·h-1, carbonization pressure is normal pressure～6MPa.
12. catalyst activity components as claimed in claim 9, it is characterised in that for one-step method from syngas coproduction mixed alcohol And alpha-olefin, reaction condition is: the unstripped gas H that reaction uses2/ CO mol ratio is 0.5～5, and reaction temperature is 200～300 DEG C, Reaction pressure is normal pressure～6MPa, and reaction velocity is 500～10000ml g-1·h-1。
13. purposes as claimed in claim 12, it is characterised in that described reaction is carried out in fixed bed or slurry bed system.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107335446A (en) * 2017-07-06 2017-11-10 中国科学院上海高等研究院 A kind of cobalt-base catalyst and its preparation and application that mixed alcohol is produced for one-step method from syngas
CN107362802A (en) * 2017-07-06 2017-11-21 中国科学院上海高等研究院 A kind of synthesis gas is converted into catalyst of alkene and its preparation method and application
CN108212167A (en) * 2017-12-31 2018-06-29 中海油天津化工研究设计院有限公司 It is a kind of for catalyst of low carbon alcohol by synthetic gas and its preparation method and application
CN111036282A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and method for preparing α -olefin from synthesis gas
CN111420674A (en) * 2020-04-09 2020-07-17 中国科学院上海高等研究院 Catalyst for directly synthesizing alcohol aldehyde oxygen-containing product by synthesis gas one-step method and application
CN112275304A (en) * 2020-11-09 2021-01-29 济南大学 Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104772150A (en) * 2014-01-15 2015-07-15 中国科学院上海高等研究院 Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof
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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104772150A (en) * 2014-01-15 2015-07-15 中国科学院上海高等研究院 Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof
CN105582970A (en) * 2014-10-27 2016-05-18 中国科学院大连化学物理研究所 Catalyst for low-carbon mixed alcohol with synergistic gas as raw material and preparation method thereof

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CN107335446A (en) * 2017-07-06 2017-11-10 中国科学院上海高等研究院 A kind of cobalt-base catalyst and its preparation and application that mixed alcohol is produced for one-step method from syngas
CN107362802A (en) * 2017-07-06 2017-11-21 中国科学院上海高等研究院 A kind of synthesis gas is converted into catalyst of alkene and its preparation method and application
CN107335446B (en) * 2017-07-06 2020-10-09 中国科学院上海高等研究院 Cobalt-based catalyst for preparing mixed alcohol from synthesis gas by one-step method and preparation and application thereof
CN108212167A (en) * 2017-12-31 2018-06-29 中海油天津化工研究设计院有限公司 It is a kind of for catalyst of low carbon alcohol by synthetic gas and its preparation method and application
CN111036282A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and method for preparing α -olefin from synthesis gas
CN111036282B (en) * 2018-10-15 2022-09-27 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and method for preparing alpha-olefin from synthesis gas
CN111420674A (en) * 2020-04-09 2020-07-17 中国科学院上海高等研究院 Catalyst for directly synthesizing alcohol aldehyde oxygen-containing product by synthesis gas one-step method and application
CN111420674B (en) * 2020-04-09 2023-03-21 中国科学院上海高等研究院 Catalyst for directly synthesizing alcohol aldehyde oxygen-containing product by synthesis gas one-step method and application
CN112275304A (en) * 2020-11-09 2021-01-29 济南大学 Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof
CN112275304B (en) * 2020-11-09 2023-03-24 济南大学 Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof
CN114146710A (en) * 2021-12-02 2022-03-08 中国科学院上海高等研究院 Reverse water gas reaction catalyst and preparation method and application thereof
CN114146710B (en) * 2021-12-02 2023-10-27 中国科学院上海高等研究院 Reverse water gas reaction catalyst and preparation method and application thereof

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